CN108885397B

CN108885397B - Surface treatment method and surface treatment liquid

Info

Publication number: CN108885397B
Application number: CN201780021452.XA
Authority: CN
Inventors: 先崎尊博
Original assignee: Tokyo Ohka Kogyo Co Ltd
Current assignee: Tokyo Ohka Kogyo Co Ltd
Priority date: 2016-03-30
Filing date: 2017-03-23
Publication date: 2022-03-01
Anticipated expiration: 2037-03-23
Also published as: JPWO2017170167A1; JP6609370B2; CN108885397A; WO2017170167A1; KR20180129803A; TW201807150A; KR102391565B1; TWI737707B

Abstract

The present invention provides: a surface treatment method capable of favorably hydrophilizing or hydrophobizing the surface of an object to be treated and forming a region having a high surface treatment effect and a region having a low surface treatment effect on the object to be treated; and a surface treatment liquid suitably usable in the surface treatment method. In a surface treatment method for cleaning a coating film formed by a photosensitive surface treatment liquid which has been exposed and baked to form a thin film having a surface modification function with a film thickness of 10nm or less, a photosensitive surface treatment liquid contains (A) a resin, (B) a photoacid generator, and (C) a solvent, the resin (A) has a functional group I which is at least 1 group selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group, and a functional group II which is a hydrophilic group or a hydrophobic group other than the functional group I, and the photoacid generator (B) generates a strong acid having a pKa of 1 or less by the action of light.

Description

Surface treatment method and surface treatment liquid

Technical Field

The present invention relates to a surface treatment method and a surface treatment liquid suitably usable in the surface treatment method.

Background

Conventionally, surface properties of various articles have been modified using various surface treatment liquids. In surface modification, there is a great demand for hydrophilization or hydrophobization of the surface of an article, and various surface treatment methods for hydrophilization or hydrophobization and surface treatment liquids that can be used in the methods have been proposed.

As the surface treatment method, for example, a method of imparting hydrophilicity and antifouling property to the surface of a coating film using a surface conditioner containing a copolymer having a weight average molecular weight of 1500 to 50000 obtained by copolymerizing at least an acrylamide monomer and a mono (meth) acrylate monomer having a siloxy group having a specific skeleton has been proposed (patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 5437523

Disclosure of Invention

Problems to be solved by the invention

However, when hydrophilization treatment is performed using the surface conditioner described in patent document 1, even if the surface of the object to be treated is treated with a solution containing only the surface conditioner, the following may occur: the surface conditioner is difficult to adhere to the surface of the object to be treated, and it is difficult to obtain a desired hydrophilization effect.

Therefore, in the method described in patent document 1, a liquid in which a resin such as an acrylic resin, a polyester resin, a polyurethane resin, an alkyd resin, an epoxy resin, or a polyamine resin is added as a film-forming component to a solution of a surface conditioner is used as a surface treatment liquid.

In addition, when the surface treatment liquid containing the surface conditioner and the film-forming component described in patent document 1 is used, the surface of the object to be treated is covered with the film containing the resin, and therefore, even if favorable hydrophilization occurs, useful surface characteristics of the object to be treated are impaired.

Depending on the use of the material subjected to the surface treatment, the effect of the surface treatment may be different between the position where the surface treatment is to be performed and the position where the surface treatment is not to be performed. It is desirable that the surface-treated site and the non-surface-treated site are patterned finely.

However, in the method using the surface conditioner used in the method described in patent document 1, it is difficult to provide a difference in the effect of the surface treatment on each part, and it is also difficult to finely and precisely apply the surface treatment agent in portions to provide a surface-treated position and a non-surface-treated position. As a result, it is difficult to provide a difference in the effect of the surface treatment between the position where the surface treatment should be performed and the position where the surface treatment should not be performed by the method described in patent document 1.

The present invention has been made in view of the above problems, and an object of the present invention is to provide: a surface treatment method capable of forming a region having a high surface treatment effect and a region having a low surface treatment effect on an object to be treated while satisfactorily hydrophilizing or hydrophobizing the surface of the object to be treated without including a film-forming resin; and a surface treatment liquid suitably usable in the surface treatment method.

Means for solving the problems

The present inventors have found that the above problems can be solved by a surface treatment method for cleaning a coating film formed from a photosensitive surface treatment liquid that has been exposed and baked to form a thin film having a surface modification function with a film thickness of 10nm or less, wherein the photosensitive surface treatment liquid contains (a) a resin, (B) a photoacid generator, and (C) a solvent, the resin (a) contains a functional group I that is at least 1 group selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group, and a functional group II that is a hydrophilic group or a hydrophobic group other than the functional group I, and the photoacid generator (B) contains a compound that generates a strong acid having a pKa of 1 or less by the action of light, and have completed the present invention. Specifically, the present invention provides the following.

A first aspect of the present invention is a surface treatment method using a photosensitive surface treatment liquid, including the steps of:

a step of applying a photosensitive surface treatment liquid to the surface of the object to be treated to form a coating film,

a step of exposing at least a part of the coating film,

a step of baking the coating film which has been exposed, and

cleaning the baked coating film to form a thin film having a thickness of 10nm or less at the exposed position on the surface of the object,

the photosensitive surface treatment liquid comprises (A) a resin, (B) a photoacid generator, and (C) a solvent,

(A) the resin has a functional group I which is at least one group selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group, and a functional group II which is a hydrophilic group or a hydrophobic group other than the functional group I,

(B) the photoacid generator generates a strong acid having a pKa of 1 or less.

The second aspect of the present invention is a photosensitive surface treatment liquid that can be used in the surface treatment method according to the first aspect, and that comprises (a) a resin, (B) a photoacid generator, and (C) a solvent,

(B) the photoacid generator generates a strong acid having a pKa of 1 or less.

The third embodiment of the present invention is a photosensitive surface treatment liquid comprising (A) a resin, (B) a photoacid generator, and (C) a solvent,

(B) the photoacid generator generates a strong acid having a pKa of 1 or less.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention enables the surface of an object to be treated to be favorably hydrophilized or hydrophobized without including a film-forming resin, and enables the object to be treated to have a region with a high surface treatment effect and a region with a low surface treatment effect.

Detailed Description

Surface treatment method

Hereinafter, a surface treatment method using the photosensitive surface treatment liquid will be described.

The surface treatment method comprises the following steps:

a step of exposing at least a part of the coating film,

a step of baking the coating film which has been exposed, and

and cleaning the baked coating film to form a thin film having a thickness of 10nm or less at the exposed position on the surface of the object.

As the photosensitive surface treatment liquid (hereinafter, also referred to as "treatment liquid"), a treatment liquid containing (a) a resin, (B) a photoacid generator, and (C) a solvent,

(B) the photoacid generator generates a strong acid having a pKa of 1 or less.

The photosensitive surface treatment liquid and the steps included in the surface treatment method will be described below.

< photosensitive surface treating liquid >

Hereinafter, essential components or optional components contained in the photosensitive surface treatment liquid will be described.

[ (A) resin ]

(A) The resin has a functional group I which is 1 or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group. The strong acid having a pKa of 1 or less generated by the photoacid generator (B) described later can enhance the reactivity or interaction between the functional group I and the surface of the non-treatment object, and thereby the resin (a) is bonded or attached to the surface of the treatment object.

(A) The resin has a functional group II as a hydrophilic group or a hydrophobic group other than the functional group I. When the treatment liquid containing the resin (a) having a hydrophilic group is used, hydrophilization treatment can be performed, and when the treatment liquid containing the resin (a) having a hydrophobic group is used, hydrophobization treatment can be performed.

The hydrophilic group or the hydrophobic group is not particularly limited as long as it is a functional group which has been conventionally considered as a hydrophilic group or a hydrophobic group by those skilled in the art, and can be appropriately selected from them.

(A) The kind of the resin is not particularly limited as long as the (a) resin has a prescribed functional group and is soluble in the (C) solvent. Examples of the resin (a) include (meth) acrylic resins, Novolac resins, polyester resins, polyamide resins, polyimide resins, polyamideimide resins, silicone resins, and the like. Among these resins, (meth) acrylic resins are preferred in terms of easy introduction of functional groups and easy adjustment of the content ratio of the units having functional groups.

Specific examples of the hydrophilic group include a polyoxyalkylene group (e.g., a polyoxyethylene group, a polyoxypropylene group, a polyoxyalkylene group in which an oxyethylene group and an oxypropylene group are bonded in a block or randomly), an amino group, a carboxyl group, a hydroxyl group, and a sulfonic acid group. In addition, organic groups containing these groups are also preferable as the hydrophilic group.

When the hydrophilic group is an acidic group, the acidic group may form a salt. The cation constituting the salt is not particularly limited, and may be a metal ion or an organic cation. As the cation, a metal ion is preferable, an alkali metal ion is more preferable, and a sodium ion or a potassium ion is particularly preferable.

(A) When the resin has a hydrophilic group or a hydrophobic group containing a hydroxyl group, a cyano group, and a carboxyl group as the functional group II, the hydroxyl group, the cyano group, or the carboxyl group contained in the hydrophilic group or the hydrophobic group also functions as the functional group I.

Therefore, when the resin (a) has a hydrophilic group or a hydrophobic group containing a hydroxyl group, a cyano group, and a carboxyl group as the functional group II, the resin (a) may not have the functional group I.

The hydrophilic group containing a hydroxyl group and a carboxyl group includes a hydroxyl group itself and a carboxyl group itself.

From the viewpoint of excellent hydrophilization effect of the treatment liquid, a group represented by the following formula (a1) is preferable as the hydrophilic group.

-NH-R¹···(A1)

(in the formula (A1), R¹Is an alkyl group having 1 to 4 carbon atoms substituted with 1 or more groups selected from the group consisting of an amino group, a sulfonic acid group and a hydroxyl group, or a hydrogen atom. )

R as a hydrophilic group represented by the formula (A1)¹Specific examples of (A) include an amino group and a group represented by the following formula.

[ chemical formula 1]

[ chemical formula 2]

[ chemical formula 3]

R in the hydrophilic group represented by the above formula (A1)¹In the specific examples of (a) and (b), the following groups are more preferable.

[ chemical formula 4]

R in the hydrophilic group represented by the above formula (A1)¹In the specific examples of (a) and (b), the following groups are particularly preferred.

[ chemical formula 5]

Specific examples of the hydrophobic group include a fluorinated hydrocarbon group, a silyl group, a siloxane group, an alkyl group having 6 to 20 carbon atoms, and an aromatic hydrocarbon group having 10 to 20 carbon atoms.

As the fluorinated hydrocarbon group, those described later with respect to the formula (A3) are preferable.

Preferable examples of the silyl group include a group represented by the formula (a4) described later wherein n is 0. Specific examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, and a triphenylsilyl group.

The siloxane group may be linear or branched. The siloxane group may be a group having a valence of 1 or a polyvalent group having a valence of 2 or more. Therefore, the so-called organosiloxane compound belongs to a compound having a siloxane group as a hydrophobic group. Preferable examples of the siloxane group include a group represented by the formula (a4) described later wherein n is 1 or more.

The resin (a) is preferably a polymer of a monomer having an unsaturated bond, because various functional groups can be easily introduced and the amount of the functional groups can be easily adjusted. The polymer may be a homopolymer or a copolymer.

In this case, the functional group I of the resin (A) is preferably a group derived from a monomer represented by the following formula (A2) or the following formula (A2-1).

CH₂＝CR²-(R³)_a-CO-R⁴···(A2)

(in the formula (A2), R²Is a hydrogen atom or a methyl group, R³Is a 2-valent hydrocarbon radical, a is 0 or 1, R⁴is-OH, -O-R⁵or-NH-R⁵，R⁵Is a hydrocarbon group substituted with 1 or more functional groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group. )

CH₂＝CR²-(R³)_a-SO₃X···(A2-1)

(in the formula (A2-1), R²、R³And a is the same as formula (A2), X is a hydrogen atom or an alkali metal. )

In the above formula (A2), R³Is a 2-valent hydrocarbon group. The number of carbon atoms of the 2-valent hydrocarbon group is not particularly limited within a range not interfering with the object of the present invention. R is a group derived from the fact that the resin (A) can be easily obtained and produced³The number of carbon atoms of the 2-valent hydrocarbon group(s) is preferably 1 to 20, more preferably 1 to 12, particularly preferably 1 to 10, and most preferably 1 to 6.

As R³The 2-valent hydrocarbon group in (1) may be an aliphatic group, an aromatic group, or a hydrocarbon group containing an aliphatic moiety and an aromatic moiety. When the 2-valent hydrocarbon group is an aliphatic group, the aliphatic group may be a saturated aliphatic group or an unsaturated aliphatic group. The structure of the aliphatic group may be linear, branched, or cyclic, or a combination of these structures.

As R³Preferable specific examples of the (B) include methylene, ethane-1, 2-diyl, ethane-1, 1-diyl, propane-1, 3-diyl, propane-1, 1-diyl, propane-2, 2-diyl, n-butane-1, 4-diyl, n-pentane-1, 5-diyl, n-hexane-1, 6-diyl and n-heptane-1, 7-diyl, n-octane-1, 8-diyl, n-nonane-1, 9-diyl, n-decane-1, 10-diyl, o-phenylene, m-phenylene, p-phenylene, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, naphthalene-1, 4-diyl, biphenyl-4, 4' -diyl, and the like.

R⁴is-OH, -O-R⁵or-NH-R⁵，R⁵Is a hydrocarbon group substituted with 1 or more functional groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group.

Form R⁵The hydrocarbon group of the main skeleton of the group (b) may be a linear, branched or cyclic aliphatic group, or may be an aromatic hydrocarbon group.

The number of carbon atoms of the linear, branched or cyclic aliphatic group is preferably 1 to 20, more preferably 1 to 12.

Preferable examples of the linear or branched aliphatic group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups.

Preferred examples of the cyclic aliphatic group include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, groups obtained by removing 1 hydrogen atom from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane, and groups obtained by removing 1 hydrogen atom from C1-C4 alkyl substituents of these polycycloalkanes.

Preferred examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group. The aromatic hydrocarbon group may be substituted with a C1-C4 alkyl group such as methyl group or ethyl group.

As a particularly preferred specific example of the unit derived from the monomer represented by the formula (A2), the following units a2-1 to a2-9 can be mentioned. Among the units a2-1 to a2-9 described below, the units a2-1 to a2-4 are more preferable.

[ chemical formula 6]

Preferred examples of the monomer represented by the formula (A2-1) include p-vinylbenzenesulfonic acid, sodium p-vinylbenzenesulfonic acid, potassium p-vinylbenzenesulfonic acid, m-vinylbenzenesulfonic acid, sodium m-vinylbenzenesulfonic acid, potassium m-vinylbenzenesulfonic acid, vinylsulfonic acid, sodium vinylsulfonate and potassium vinylsulfonate.

(A) When the resin has a hydrophobic group as the functional group II, the functional group II is preferably derived from a monomer represented by the following formula (a 3).

CH₂＝CR²-(CO-O)_b-R⁶···(A3)

(in the formula (A3), R²Is a hydrogen atom or a methyl group, b is 0 or 1, R⁶Is a fluorinated hydrocarbon group or a group represented by the following formula (A4),

-SiR⁷R⁸-(-O-SiR⁷R⁸-)_n-R⁹...(A4)

R⁷、R⁸and R⁹Each independently a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 0 or more. )

In the formula (A3), R⁶In the case of a fluorinated hydrocarbon group, the hydrocarbon group constituting the main skeleton of the fluorinated hydrocarbon group and R constituting the above-mentioned group⁵The hydrocarbon group of the main skeleton of the group (1) is the same. The fluorinated hydrocarbon group may be a group in which all hydrogen atoms of the hydrocarbon group are substituted by fluorine atoms.

With respect to as R⁶Specific example of the fluorinated hydrocarbon group of (3) includes-CF₃、-CF₂CF₃、-(CF₂)₂CF₃、-(CF₂)₃CF₃、-(CF₂)₄CF₃、-(CF₂)₅CF₃、-(CF₂)₆CF₃、-(CF₂)₇CF₃、-(CF₂)₈CF₃、-(CF₂)₉CF₃、-CH₂CF₃、-CH₂CF₂CF₃、-CH₂(CF₂)₂CF₃、-CH₂(CF₂)₃CF₃、-CH₂(CF₂)₄CF₃、-CH₂(CF₂)₅CF₃、-CH₂(CF₂)₆CF₃、-CH₂(CF₂)₇CF₃、-CH₂(CF₂)₈CF₃、-CH₂CH₂CF₃、-CH₂CH₂CF₂CF₃、-CH₂CH₂(CF₂)₂CF₃、-CH₂CH₂(CF₂)₃CF₃、-CH₂CH₂(CF₂)₄CF₃、-CH₂CH₂(CF₂)₅CF₃、-CH₂CH₂(CF₂)₆CF₃、-CH₂CH₂(CF₂)₇CF₃、-CH₂CF₂H、-CH₂CF₂CF₂H、-CH₂(CF₂)₂CF₂H、-CH₂(CF₂)₃CF₂H、-CH₂(CF₂)₄CF₂H、-CH₂(CF₂)₅CF₂H、-CH₂(CF₂)₆CF₂H、-CH₂(CF₂)₇CF₂H、-CH₂(CF₂)₈CF₂H、-CH₂CH₂CF₂H、-CH₂CH₂CF₂CF₂H、-CH₂CH₂(CF₂)₂CF₂H、-CH₂CH₂(CF₂)₃CF₂H、-CH₂CH₂(CF₂)₄CF₂H、-CH₂CH₂(CF₂)₅CF₂H、-CH₂CH₂(CF₂)₆CF₂H、-CH₂CH₂(CF₂)₇CF₂H. and-CH (CF)₃)₂And the like chain fluoroalkyl groups; fluorinated aromatic hydrocarbon groups such as pentafluorophenyl, o-trifluoromethylphenyl, m-trifluoromethylphenyl, and p-trifluoromethylphenyl; a fluorinated alicyclic group such as octafluoroadamantyl.

In the formula (A3), R⁶When it is a group represented by the formula (A4), R⁷、R⁸And R⁹Each independently is preferably methyl, ethyl, or phenyl, more preferably R⁷、R⁸And R⁹Are all methyl.

In the formula (a4), the upper limit of n is not particularly limited within a range not interfering with the object of the present invention. n is preferably an integer of 0 to 35, more preferably an integer of 0 to 10.

Particularly preferred specific examples of the unit having a hydrophobic group derived from the monomer represented by the formula (A3) include the units a3-1 to a 3-24. Among the units described below, the units a3-8, a3-12, a3-18, a3-19, and a3-22 are more preferable.

[ chemical formula 7]

When the resin (a) has a hydrophilic group as the functional group II, the functional group II is preferably derived from a monomer represented by the following formula (a 5).

CH₂＝CR²-CO-NH-R¹···(A5)

(in the formula (A5), R¹Is an alkyl group having 1 to 4 carbon atoms substituted with 1 or more groups selected from the group consisting of an amino group, a sulfonic acid group and a hydroxyl group, or a hydrogen atom, R²Is a hydrogen atom or a methyl group. )

In the formula (A5), R is¹As described above.

Particularly preferred examples of the unit having a hydrophilic group derived from the monomer represented by the formula (A5) include the units a5-1 to a 5-5. Among the units described below, the units a5-1 to a5-4 are more preferable.

[ chemical formula 8]

(A) When the resin is a polymer of a monomer having an unsaturated bond, the polymer may contain a unit derived from the monomer represented by the above formula (a2), a unit derived from the monomer represented by the formula (A3), and a structural unit other than the unit derived from the monomer represented by the formula (a5) within a range not to impair the object of the present invention.

Examples of the other structural units include those derived from methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, N-propyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, N-pentyl (meth) acrylate, isoamyl (meth) acrylate, phenyl (meth) acrylate, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-N-butyl (meth) acrylamide, N-N-pentyl (meth) acrylamide, N-isopentyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-dimethyl (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylate, N-N-butyl (meth) acrylamide, N-N-pentyl (meth) acrylamide, N-isopentyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-dimethyl (meth) acrylamide, N-pentyl (meth) acrylamide, N-butyl (meth) acrylamide, N-pentyl (meth) acrylamide, N-hexyl (meth) acrylamide, N, N, N-diethyl (meth) acrylamide, N-di-N-propyl (meth) acrylamide, N-di-N-butyl (meth) acrylamide, N-di-N-pentyl (meth) acrylamide, styrene, α -methylstyrene, β -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and chlorostyrene.

(A) When the resin is a polymer of a monomer having an unsaturated bond, the molar ratio of the structural unit derived from the monomer represented by formula (a2) in all the structural units contained in the polymer is preferably 0.1 to 50 mol%, more preferably 1 to 20 mol%, and particularly preferably 1 to 15 mol%.

(A) When the resin is a polymer of a monomer having an unsaturated bond, the molar ratio of the structural unit derived from the monomer represented by the formula (A3) or (a5) in all the structural units contained in the polymer is preferably 50 to 99.9 mol%, more preferably 60 to 99 mol%, and particularly preferably 70 to 99 mol%.

However, when the structural unit derived from the monomer represented by the formula (a5) contains any one of a hydroxyl group, a cyano group, and a carboxyl group, the ratio of the structural unit derived from the monomer represented by the formula (a5) to the total structural units contained in the polymer may be 100%.

Further, a siloxane compound represented by the following formula (a6) is also preferable as the resin (a).

A¹-SiR¹⁰R¹¹-O-(-SiR¹⁰A²-O-)_p-SiR¹⁰R¹¹A³...(A6)

(in the formula (A6), R¹⁰And R¹¹Each independently a hydrocarbon group having 1 to 6 carbon atoms, A¹、A²And A³Each independently a hydroxyl group, a cyano group, a carboxyl group, or a hydrocarbon group having 1 to 6 carbon atoms, A¹、A²And A³At least 1 of them is a hydroxyl group, a cyano group or a carboxyl group, and p is an integer of 0 or more. )

The siloxane compound represented by formula (a6) belongs to the (a) resin having a siloxane group as a hydrophobic group.

A plurality of R's in the formula (A6)¹⁰May be the same or different. In addition, in the formula (A6), there are a plurality of R' s¹¹May be the same or different.

R¹⁰And R¹¹Each independently is preferably methyl, ethyl, or phenyl, more preferably R¹⁰And R¹¹Are all methyl.

In addition, A¹、A²And A³When the alkyl group has 1 to 6 carbon atoms, A¹、A²And A³Each independently is preferably methyl, ethyl, or phenyl, more preferably methyl.

The amount of the resin (a) contained in the treatment liquid is not particularly limited within a range not interfering with the object of the present invention, and may be appropriately determined in consideration of the coatability of the treatment liquid and the like. Typically, the amount of the (a) resin in the treatment liquid is preferably the following amount: the relationship between the amount of the resin (a) and the amount of the solvent (C) in the treatment solution is as follows.

The amount of the solvent (C) to be described later is preferably 100 to 100000 parts by mass, more preferably 500 to 80000 parts by mass, and particularly preferably 1000 to 60000 parts by mass, based on 100 parts by mass of the resin in the treatment liquid.

[ (B) photoacid generators ]

The treatment liquid contains (B) a photoacid generator. (B) The photoacid generator generates a strong acid having a pKa of 1 or less by the action of light. The pKa is a value in water.

The strong acid generated by the photo-generator (B) acts on the functional group I of the resin (A), thereby promoting the adhesion or bonding of the resin (A) to the surface of the object to be treated.

(B) The kind of the photoacid generator is not particularly limited as long as it generates a strong acid having a pKa of 1 or less by the action of light. The photoacid generator (B) may be used in combination of 2 or more.

Preferred examples of the strong acid generated by the photoacid generator (B) include fluoroaliphatic carboxylic acids (e.g., trifluoroacetic acid), fluorosulfonic acids, alkanesulfonic acids having 1 to 30 carbon atoms (e.g., methanesulfonic acid, dodecanesulfonic acid, etc.), arylsulfonic acids (e.g., benzenesulfonic acid, p-toluenesulfonic acid, etc.), fluoroalkanesulfonic acids having 1 to 30 carbon atoms (e.g., trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, and tridecafluorohexanesulfonic acid), bissulfonylimide compounds, cyclic sulfonylimide compounds in which 2 sulfonyl groups are connected by a fluoroalkylene group, and N-acylfluoroalkanesulfonamides.

When the strong acid comprises a fluoroalkyl group or a fluoroalkylene group, these groups may be a partially fluorinated fluoroalkyl group or a fluoroalkylene group, or a fully fluorinated perfluoroalkyl group or a perfluoroalkylene group.

Among these strong acids, preferred are fluorosulfonic acid, alkanesulfonic acid having 1 to 30 carbon atoms, fluoroalkanesulfonic acid having 1 to 30 carbon atoms, bis (fluoroalkylsulfonyl) imide acid, cyclic sulfoneimide acid in which 2 sulfonyl groups are connected to each other by a fluoroalkylene group, and N-acylfluoroalkanesulfonamide, and preferred are fluoroalkanesulfonic acid having 1 to 30 carbon atoms, bissulfonylimide compound, cyclic sulfonylimide compound in which 2 sulfonyl groups are connected to each other by a fluoroalkylene group, and N-acylfluoroalkanesulfonamide.

As the fluoroalkanesulfonic acid having 1 to 30 carbon atoms, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid and the like are preferable.

The bissulfonylimide compound is preferably a compound represented by the following formula (B1).

[ chemical formula 9]

In the formula (B1), X¹And X²Each independently represents a hydrocarbon group substituted with at least 1 electron-withdrawing group. The hydrocarbon group may be substituted with various groups other than an electron-withdrawing group within a range that does not impair the strong acidity of the compound represented by formula (B1). X¹And X²The number of carbon atoms of (A) is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 7.

As the hydrocarbon group substituted with an electron-withdrawing group, a fluoroalkyl group or an aryl group having a nitro group is preferable. The fluoroalkyl group may be linear or branched, and may be cyclic. The fluoroalkyl group is preferably a perfluoroalkyl group which is completely fluorinated. The aryl group having a nitro group is preferably an o-nitrophenyl group, a m-nitrophenyl group or a p-nitrophenyl group, and more preferably a p-nitrophenyl group.

Preferable specific examples of the compound represented by the formula (B1) include compounds of the following formula.

[ chemical formula 10]

As the cyclic sulfimide compound in which 2 sulfonyl groups are connected by a fluoroalkylene group, a compound represented by the following formula (B2) is preferable.

[ chemical formula 11]

In the formula (B2), X³Represents a linear or branched alkylene group in which at least 1 hydrogen atom is substituted by a fluorine atom. X³The number of carbon atoms of (A) is preferably 2 to 6, more preferably 3 to 5, and particularly preferably 3.

Preferable specific examples of the compound represented by the formula (B2) include compounds of the following formula.

[ chemical formula 12]

As the N-acylfluoroalkanesulfonamide, a compound represented by the following formula (B3) is preferable.

[ chemical formula 13]

In the formula (B3), X⁴Represents a linear or branched alkyl group in which at least 1 hydrogen atom is substituted by a fluorine atom. X⁴The number of carbon atoms of (A) is preferably 1 to 10, more preferably 1 to 7, and particularly preferably 1 to 3.

X⁵Is a hydrocarbyl group. The hydrocarbon group and R constituting the above⁵The hydrocarbon group of the main skeleton of the group (1) is the same.

Preferable specific examples of the compound represented by the formula (B3) include compounds of the following formula.

[ chemical formula 14]

As the (B) photoacid generator, a compound which can generate the preferred strong acid described above is preferable.

As the compound, an onium salt compound containing an anion derived from the above strong acid and an onium ion is preferable. The onium ion is preferably an iodonium ion or a sulfonium ion, and more preferably a sulfonium ion.

Preferable examples of the onium ion include triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonium (sulfonio)) phenyl ] sulfide, bis [4- { bis [4- (2-hydroxyethoxy) phenyl ] sulfonium } phenyl ] sulfide, bis {4- [ bis (4-fluorophenyl) sulfonium ] phenyl } sulfide, 4- (4-benzoyl-2-chlorophenylthio) phenyl bis (4-fluorophenyl) sulfonium, 7-isopropyl-9-oxo-10-thia-9, 10-dihydroanthracen-2-yl-di-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9, 10-dihydroanthracen-2-yl-diphenylsulfonium, and mixtures thereof, 2- [ (diphenyl) sulfonium ] thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio ] phenyl di-p-tolylsulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylbenzoylmethylsulfinyl, phenyl [4- (4-biphenylthio) phenyl ] 4-biphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl ] 3-biphenylsulfonium, [4- (4-acetylphenylsulfanyl) phenyl ] diphenylsulfonium, octadecylmethylbenzoylmethylsulfonium, diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, and the like, Bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxy) phenyliodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, or 4-isobutylphenyl (p-tolyl) iodonium, and the like.

Further, a sulfonium ion represented by the following formula (B4) is also preferable as an onium ion constituting the onium salt.

[ chemical formula 15]

In the above formula (B4), R^b1Each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, a halogen atom, an aryl group which may have a substituent, and an arylcarbonyl group. X⁶The structure is represented by the following formula (B5).

[ chemical formula 16]

In the above formula (B5), X⁷X represents a 2-valent group of an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a heterocyclic compound having 8 to 20 carbon atoms⁷Can be substituted with at least 1 kind selected from the group consisting of alkyl with 1-8 carbon atoms, alkoxy with 1-8 carbon atoms, aryl with 6-10 carbon atoms, hydroxyl, cyano, nitro and halogen. X⁸represents-O-, -S-, -SO-, -SO₂-、-NH-、-NR^b2-, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group. h represents the number of repeating units of the structure in parentheses. h + 1X⁶And h X⁷Each may be the same or different. R^b2Is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

Specific examples of the sulfonium ion represented by the formula (B4) include 4- (phenylthio) phenyldiphenylsulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl ] 4-biphenylsulfonium, phenyl [4- (4-biphenylthio) phenyl ] 3-biphenylsulfonium, [4- (4-acetylphenylthio) phenyl ] diphenylsulfonium, and diphenyl [4- (p-terphenylthio) phenyl ] diphenylsulfonium.

In addition, an onium salt containing a cation portion having a naphthalene ring and an anion portion derived from the above strong acid is also preferable as (B) the photoacid generator. The "having a naphthalene ring" means having a structure derived from naphthalene, means a structure having at least 2 rings, and the aromaticity thereof is maintained. The naphthalene ring may have a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. The structure derived from the naphthalene ring may be a 1-valent group (free valence is 1), or may be a 2-valent group (free valence is 2) or more, and is preferably a 1-valent group (in this case, the free valence is counted excluding a portion bonded to the substituent). The number of naphthalene rings is preferably 1 to 3.

The onium ion having a naphthalene ring is preferably an onium ion represented by the following formula (B6).

[ chemical formula 17]

In the above formula (B6), R^b3、R^b4、R^b5At least 1 of the (A) groups (B) is a group represented by the following formula (B7), and the rest is a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group which may have a substituent, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Or, R^b3、R^b4、R^b5Wherein 1 of the groups is a group represented by the following formula (B7), and the remaining 2 groups may be each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and the terminal of each group is bonded to form a cyclic group.

[ chemical formula 18]

In the above formula (B7), R^b6、R^b7Each independently represents a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms, R^b8Represents a single bond or a linear or branched alkylene group which may have a substituent having 1 to 6 carbon atoms. 1 and m each independently represent an integer of 0 to 2, and 1+ m is 3 or less. Wherein R is^b6When a plurality of them exist, they may be the same or different from each other. In addition, R^b7When a plurality of them exist, they may be the same or different from each other.

From the viewpoint of stability of the compound, the above R^b3、R^b4、R^b5In the formula (B7), the number of the groups represented by the formula (B7) is preferably 1, and the remainder may be a linear or branched alkylene group having 1 to 6 carbon atoms, and the ends of the groups are bonded to form a cyclic group. In this case, the 2 alkylene groups include a sulfur atom and form a 3-to 9-membered ring. The number of atoms constituting the ring (including sulfur atoms) is preferably 5 to 6.

Examples of the substituent that the alkylene group may have include an oxygen atom (in this case, a carbonyl group is formed together with a carbon atom constituting the alkylene group), a hydroxyl group, and the like.

Examples of the substituent which the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, a linear or branched alkyl group having 1 to 6 carbon atoms, and the like.

Preferred structures of these cation portions include structures represented by the following formulae (B8) and (B9), and a structure represented by the following formula (B9) is particularly preferred.

[ chemical formula 19]

The content of the photoacid generator (B) in the treatment liquid is not particularly limited, and the surface treatment by the treatment liquid may be favorably performed. The content of the photoacid generator (B) in the treatment liquid is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the resin (a).

[ (C) solvent ]

(C) The solvent is not particularly limited as long as the (a) resin and the (B) photoacid generator are soluble in the solvent. The treatment liquid may contain the resin (a) and the photoacid generator in an undissolved state, as long as predetermined amounts of the resin (a) and the photoacid generator (B) are dissolved in the treatment liquid. It is preferable that the (a) resin and the (B) photoacid generator are completely dissolved in the treatment solution.

When the treatment liquid contains insoluble matter, the insoluble matter may adhere to the surface of the object to be treated during the surface treatment. In this case, insoluble substances adhering to the surface of the object to be treated can be removed by cleaning the surface of the object to be treated by a method described later.

(C) The solvent may be water, an organic solvent, or an aqueous solution of an organic solvent.

Specific examples of the organic solvent that can be used as the solvent (C) include:

C1-C5 alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, n-pentanol, sec-pentanol, isopentanol, and tert-pentanol;

sulfoxides such as dimethyl sulfoxide;

sulfones such as dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone and tetramethylene sulfone;

amides such as N, N-dimethylformamide, N-methylformamide, N-dimethylacetamide, N-methylacetamide, and N, N-diethylacetamide;

lactams such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, and N-hydroxyethyl-2-pyrrolidone;

imidazolinones such as 1, 3-dimethyl-2-imidazolidinone, 1, 3-diethyl-2-imidazolidinone, and 1, 3-diisopropyl-2-imidazolidinone;

dialkyl glycol ethers such as dimethyl glycol ether (dimethyl glycol), dimethyl diglycol ether, dimethyl triethylene glycol ether, methyl ethyl diglycol ether, diethyl glycol ether, and triethylene glycol butyl methyl ether;

(poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc.;

(poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate;

other ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisoamyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran;

ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

alkyl lactate esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl 2-oxobutyrate and other esters;

lactones such as β -propiolactone, γ -butyrolactone, and δ -valerolactone;

straight-chain, branched, or cyclic aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, n-nonane, methyloctane, n-decane, n-undecane, n-dodecane, 2, 4, 6, 6-pentamethylheptane, 2, 4, 4, 6, 8, 8-heptamethylnonane, cyclohexane, and methylcyclohexane;

aromatic hydrocarbons such as benzene, toluene, xylene, 1, 3, 5-trimethylbenzene, and naphthalene;

terpenes such as p-menthane (p-menthane), diphenyl menthane (diphenyl menthane), limonene (limonene), terpinene (terpinene), camphane (bornane), norbornane (norbomane) and pinane (pinane); and so on.

(C) When the solvent is a mixed solvent of water and an organic solvent, the content of the organic solvent in the (C) solvent is preferably 10% by mass or more, and more preferably 20% by mass or more.

< other ingredients >

The treatment liquid may contain various components other than the resin (a), the photoacid generator (B), and the solvent (C) within a range not to impair the object of the present invention. Examples of the other components include a colorant, a surfactant, an antifoaming agent, and a viscosity modifier.

< method for producing treating liquid >

The method for preparing the treatment liquid is not particularly limited. Typically, the treatment liquid is prepared by uniformly mixing predetermined amounts of (a) a resin, (B) a photoacid generator, (C) a solvent, and other components as needed.

< coating film Forming step >

The surface treatment liquid described above is applied to the surface of the object to be treated to form a coating film.

The method of applying the surface treatment liquid is not particularly limited. Specific examples of the coating method include spin coating, spray coating, roll coating, and dipping. When the object to be treated is a substrate, a spin coating method is preferable as a coating method because the surface of the substrate can be uniformly hydrophilized or hydrophobized by uniformly coating the surface treatment liquid.

The material of the surface of the object to be treated to which the surface treatment liquid is applied is not particularly limited, and may be an organic material or an inorganic material.

Examples of the organic material include polyester resins such as PET resins and PBT resins, various nylons, polyimide resins, polyamideimide resins, polyolefins such as polyethylene and polypropylene, and various resin materials such as polystyrene and (meth) acrylic resins.

In addition, a photosensitive resin component or an alkali-soluble resin component contained in various resist materials is also preferable as the organic material.

Examples of the inorganic material include various metals such as glass, silicon, copper, aluminum, iron, and tungsten. The metal may be an alloy.

The material of the surface treated with the surface treatment liquid is not particularly limited, and when the material of the surface to which the surface treatment liquid is applied is an organic material, it is preferable to use a surface treatment liquid containing a resin (a) having a hydroxyl group and/or a carboxyl group as the functional group I.

When the material of the surface to which the surface treatment liquid is applied is an inorganic material, hydroxyl group, carboxyl group, and cyano group are preferable as the functional group I of the resin (a).

The shape of the object to be treated is not particularly limited. The object to be processed may be a flat substrate or may have a three-dimensional shape such as a spherical shape or a columnar shape. The surface of the object to be treated may be smooth, or may have regular or irregular irregularities.

After the surface treatment liquid is applied to the surface of the object to be treated, the applied film may be heated as necessary to remove at least a part of the solvent (C).

< Exposure Process >

The coating film formed as described above is exposed by irradiating ultraviolet light or visible light having a wavelength of 300 to 500nm, for example. The exposure is performed to the site where hydrophilization or hydrophobization is desired.

When the entire position where the coating film is formed is to be made highly hydrophilic or hydrophobic, the entire surface of the coating film is exposed. When it is desired to highly hydrophilize or hydrophobize a part of a site where a coating film is formed and to reduce the degree of hydrophilization or hydrophobization at other sites, exposure is selectively performed only for the site where highly hydrophilization or hydrophobization is desired.

The method for performing the position-selective exposure is not particularly limited, and the exposure can be performed through a photomask in general.

As a radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an argon laser, or the like can be used. The radiation includes microwave, infrared ray, visible ray, ultraviolet ray, X-ray, γ -ray, electron beam, proton beam, neutron beam, ion beam, and the like. The radiation exposure amount (exposure amount) is typically 100 to 10000mJ/cm when an ultra-high pressure mercury lamp is used, for example²。

< baking Process >

Next, the coating film that has been exposed to light is baked. Typically, the baking temperature is preferably 40 to 200 ℃, and more preferably 60 to 150 ℃. The baking time is preferably 10 to 6000 seconds, and more preferably 10 to 300 seconds.

< cleaning Process >

The baked coating film may be cleaned.

As described above, when the surface treatment liquid containing the resin (a) having a predetermined functional group and the photoacid generator (B) is applied to the surface of the object to be treated and exposed to light, the resin (a) adheres or bonds well to the surface of the object to be treated due to the action of the strong acid generated by the photoacid generator (B).

However, the resin (a) that does not adhere or bond to the surface of the object to be treated, particularly, the unexposed portion, is present in a certain amount.

However, by cleaning the coating film, the resin (a) and the like that do not adhere to the surface of the object to be treated can be washed away.

As a result, a thin film having a thickness of 10nm or less can be formed on the exposed portion of the surface of the object by cleaning.

The film thickness of the thin film can be determined using a spectroscopic ellipsometer.

When the surface treatment liquid containing the (a) resin having a hydrophilic group as the functional group II is used, washing with water is preferable. In addition, when the surface treatment liquid containing the resin (a) having a hydrophobic group as the functional group II is used, it is preferable to perform cleaning with an organic solvent. The organic solvent is preferably an organic solvent contained as the solvent (C) in the surface treatment liquid.

By drying the surface of the object to be treated after washing, a favorably hydrophilized or hydrophobized article can be obtained.

In various articles subjected to surface treatment by the above-described method, hydrophilization or hydrophobization can be performed highly only at necessary positions, while the degree of hydrophilization or hydrophobization at other positions can be reduced. Examples of the article subjected to the surface treatment include a cell culture device, a microchannel device for circulating a liquid containing a biological sample such as cells, and the like. By surface treatment, various articles can be provided with stain resistance, antifogging property, and the like.

[ examples ]

The present invention will be described in further detail below with reference to examples, but the present invention is not limited to these examples.

[ examples 1 to 10 and comparative examples 1 to 4]

In each of examples and comparative examples, the resins shown in table 1 were used as the resin (a).

The structural units A-1a to A-6a shown in Table 1 are structural units that provide a hydrophilic group or a hydrophobic group to the resin (A). In the formula A-6a, n represents the number of repetition of the unit in the parentheses.

The structural units A-1b to A-3b shown in Table 1 are units that provide a hydroxyl group, a cyano group, or a carboxyl group to the resin (A).

The structural units a-1c and a-2c shown in table 1 are structural units having no hydrophilic group, no hydrophobic group, no hydroxyl group, no cyano group, or no carboxyl group.

The compounds 1 to 4 shown in Table 1 are organosiloxane compounds having the following structures. In the formulae representing the compounds 1 to 4, n1 and n2 represent the number of repetition of the unit in each bracket.

[ chemical formula 20]

[ chemical formula 21]

[ chemical formula 22]

With respect to the following silicone compounds, the amount of hydroxyl groups of compound 1 was 58mgKOH/mol, the amount of carboxyl groups of compound 3 was 4000g/mol, and the amount of hydrogen atoms directly bonded to silicon atoms of compound 4 was 60 g/mol.

[ chemical formula 23]

[ Table 1]

	(A) Resin composition
		Example 1	A-la/A-1b (mol)Ratio) 97/3
Example 2	A-2a/a-2b (molar ratio) 95/5
		Example 3	A-3a/a-2b (molar ratio) 95/5
Example 4	A-4a/a-3b (molar ratio) 95/5
		Example 5	A-4a/a-5a/a-3b (molar ratio) 5/90/5
Example 6	A-6a/a-3b (molar ratio) 95/5
		Example 7	A-la/a-2a/a-2b (molar ratio) ═ 45/45/10
Example 8	Compound 1
		Example 9	Compound 2
Example 10	Compound 3
		Comparative example 1	A-1a/a-1c (molar ratio) 97/3
Comparative example 2	A-1a/a-2c (molar ratio) ═ 97/3
		Comparative example 3	Compound 4
Comparative example 4	A-1a/a-1b (molar ratio) 97/3

In the examples and comparative examples, the following photoacid generators B1 to B3 were used. B1 and B2 are photoacid generators that generate strong acids having pKa of 1 or less, and B3 is a photoacid generator that generates acids having pKa greater than 1.

[ chemical formula 24]

10 parts by mass of a resin (a) of the type shown in table 1 and a photoacid generator (B) of the type and amount shown in table 2 were uniformly mixed in a solvent (C) of the type and amount shown in table 2 to obtain surface treatment liquids of examples and comparative examples.

PGME in table 2 is propylene glycol monomethyl ether and PGMEA is propylene glycol monomethyl ether acetate.

The obtained surface treatment liquid was spin-coated on a glass substrate at 1000rpm for 30 seconds, and then dried at 100 ℃ for 60 seconds to obtain a coating film.

The obtained coating film was subjected to high-temperature heating at 1000mJ/cm using HMW-532D (manufactured by ORC) through a mask²The exposure is performed with the exposure amount of (1).

The coating film that had been exposed to light was baked at 100 ℃ for 60 seconds and then washed, to obtain a surface-treated glass substrate.

Examples 1 to 3, example 7, comparative example 1, comparative example 2, and comparative example 4, which used a resin having a hydrophilic group, were washed with water. For the other examples and comparative examples, cleaning was performed with PGMEA.

After drying the cleaned glass substrate, the contact angle of water of the glass substrate was measured with respect to the exposed portion and the unexposed portion, respectively. For measurement of the contact angle of water, a drop of pure water (2.0. mu.L) was dropped on the surface of the substrate subjected to surface treatment using Dropmaster700 (manufactured by Kyowa Kagaku K.K.) and measured as the contact angle 10 seconds after dropping. The results of measuring the contact angle of water are shown in table 2.

In the case of the substrate after drying, the exposed position was confirmed by a spectroscopic ellipsometer, and in the examples, the presence of a thin film having a film thickness of 10nm or less was observed, and in the comparative examples, the presence of a thin film was not observed.

[ Table 2]

As is clear from the examples, when a surface treatment liquid containing (a) a resin having a functional group I which is at least 1 group selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group, and a functional group II which is a hydrophilic group other than the functional group I or a hydrophobic group, and (B) a photoacid generator which generates a strong acid having a pKa of 1 or less is used, a coating film formed from the surface treatment liquid is exposed to light, and then baked and cleaned, whereby only the exposed position on the substrate can be favorably hydrophilized or hydrophobized.

As is clear from comparative examples 1 to 3, when the resin (a) does not have any of a hydroxyl group, a cyano group, and a carboxyl group, even if the surface treatment liquid contains the photoacid generator (B) that generates a strong acid having a pKa of 1 or less, the exposed portion cannot be hydrophilized or hydrophobized satisfactorily.

As is clear from comparative example 4, when the surface treatment liquid contains (B) the photoacid generator that generates an acid having a pKa of greater than 1, even if the resin (a) has a functional group I as a carboxyl group and a functional group II as a hydrophilic group, the exposed portion cannot be hydrophilized or hydrophobized satisfactorily.

[ examples 11 to 15]

In example 11, a surface treatment liquid was used in which 10 parts by mass of the resin (a), 0.1 part by mass of the photoacid generator (B), and 1000 parts by mass of PGMEA were uniformly mixed.

The resin contained in the surface treatment liquid of example 11 was a resin containing the aforementioned A-4a unit and A-2b unit in a molar ratio of 95: 5(A-4 a: A-2 b).

The photoacid generator (B) included in the surface treatment liquid of example 11 was the compound of B2 described above.

The contact angle of water after surface treatment was measured in the same manner as in example 1 except that the surface treatment liquid of the type shown in table 3 was used, the type of the substrate was changed to the type shown in table 3, and the entire surface of the coating film was exposed. The measurement results are shown in Table 1. In the PET film and the silicon wafer, the contact angle of water in an untreated state of the PET film was about 70 °, and the contact angle of water in an untreated state of the silicon wafer was about 10 °.

[ Table 3]

As is clear from example 11, when the resin (a) contained in the surface treatment liquid has a cyano group as the functional group I, the surface of the substrate made of the inorganic material (silicon) is favorably hydrophobized.

Examples 12 to 15 show that when the resin (a) contained in the surface treatment liquid has a hydroxyl group or a carboxyl group as the functional group I, both the surface of the substrate made of the inorganic material (silicon) and the surface of the substrate made of the organic material (PET) are hydrophobized favorably.

Claims

1. A surface treatment method using a photosensitive surface treatment liquid, comprising the steps of:

a step of applying the photosensitive surface treatment liquid to the surface of an object to be treated to form a coating film,

a step of exposing at least a part of the coating film,

a step of baking the coating film that has been exposed, and

a step of cleaning the baked coating film to remove the coating film not adhering to the surface of the object to be processed, and forming a thin film having a film thickness of 10nm or less at the exposed position on the surface of the object to be processed,

the resin (A) has a functional group I which is at least one group selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group, and a functional group II which is a hydrophilic group or a hydrophobic group other than the functional group I, and is a siloxane compound represented by the following formula (A6) or a resin: the hydrophilic group of the functional group II is a group represented by the following formula (A1) or a group derived from a monomer represented by the following formula (A2-1),

-NH-R¹···(A1)

in the formula (A1), R¹An alkyl group having 1 to 4 carbon atoms substituted with 1 or more groups selected from the group consisting of an amino group, a sulfonic acid group and a hydroxyl group, or a hydrogen atom,

CH₂＝CR²-(R³)_a-SO₃X···(A2-1)

in the formula (A2-1), R²Is a hydrogen atom or a methyl group, R³Is a 2-valent hydrocarbon group, a is 0 or 1, X is a hydrogen atom or an alkali metal,

A¹-SiR¹⁰R¹¹-O-(-SiR¹⁰A²-O-)_p-SiR¹⁰R¹¹A³···(A6)

in the formula (A6), R¹⁰And R¹¹Each independently a hydrocarbon group having 1 to 6 carbon atoms, A¹、A²And A³Each independently of the others being hydroxy, cyanoA group, a carboxyl group or a hydrocarbon group having 1 to 6 carbon atoms, A¹、A²And A³At least 1 of which is a hydroxyl group, a cyano group, or a carboxyl group, p is an integer of 0 or more,

the photoacid generator (B) generates a strong acid having a pKa of 1 or less.

2. The surface treatment method according to claim 1, wherein the exposure of the coating film is selectively performed through a photomask position.

3. The surface treatment method according to claim 1, wherein the functional group I is derived from a monomer represented by the following formula (A2),

CH₂＝CR²-(R³)_a-CO-R⁴···(A2)

in the formula (A2), R²Is a hydrogen atom or a methyl group, R³Is a 2-valent hydrocarbon radical, a is 0 or 1, R⁴is-OH, -O-R⁵or-NH-R⁵，R⁵Is a hydrocarbon group substituted with 1 or more functional groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group.

4. The surface treatment method according to claim 1, wherein the functional group II is a hydrophilic group and is derived from a monomer represented by the following formula (A5),

CH₂＝CR²-CO-NH-R¹···(A5)

in the formula (A5), R¹Is an alkyl group having 1 to 4 carbon atoms substituted with 1 or more groups selected from the group consisting of an amino group, a sulfonic acid group and a hydroxyl group, or a hydrogen atom, R²Is a hydrogen atom or a methyl group.

5. The surface treatment method according to any one of claims 1 to 4, wherein a material of a surface to which the surface treatment liquid is applied is an organic material, and the resin (A) has a hydroxyl group and/or a carboxyl group as the functional group I.

6. A photosensitive surface treatment liquid used in the surface treatment method according to any one of claims 1 to 4, comprising (A) a resin, (B) a photoacid generator, and (C) a solvent,

the resin (A) has a functional group I which is at least one group selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group, and a functional group II which is a hydrophilic group or a hydrophobic group other than the functional group I,

the photoacid generator (B) generates a strong acid having a pKa of 1 or less.

7. A photosensitive surface treatment liquid comprising (A) a resin, (B) a photoacid generator, and (C) a solvent,

the photoacid generator (B) generates a strong acid having a pKa of 1 or less,

the functional group I is derived from a monomer represented by the following formula (A2),

CH₂＝CR²-(R³)_a-CO-R⁴···(A2)

in the formula (A2), R²Is a hydrogen atom or a methyl group, R³Is a 2-valent hydrocarbon radical, a is 0 or 1, R⁴is-OH, -O-R⁵or-NH-R⁵，R⁵A hydrocarbon group substituted with 1 or more functional groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group,

the resin (A) is a siloxane compound represented by the following formula (A6) or a resin containing a hydrophilic group represented by the following formula (A1) or a hydrophilic group derived from a monomer represented by the following formula (A2-1) as the functional group II,

-NH-R¹···(A1)

in the formula (A1), R¹An alkyl group having 1 to 4 carbon atoms substituted with 1 or more groups selected from the group consisting of an amino group and a sulfonic acid group, or a hydrogen atom,

CH₂＝CR²-(R³)_a-SO₃X···(A2-1)

in the formula (A2-1), R²、R³And a is the same as formula (A2), X is a hydrogen atom or an alkali metal,

A¹-SiR¹⁰R¹¹-O-(-SiR¹⁰A²-O-)_p-SiR¹⁰R¹¹A³···(A6)

in the formula (A6), R¹⁰And R¹¹Each independently a hydrocarbon group having 1 to 6 carbon atoms, A¹And A³Each independently a hydroxyl group, a cyano group, or a hydrocarbon group having 1 to 6 carbon atoms, A²And A¹And A³Independently a hydroxyl group, a cyano group, a carboxyl group, or a hydrocarbon group having 1 to 6 carbon atoms, A¹、A²And A³At least 1 of them is a hydroxyl group, a cyano group or a carboxyl group, and p is an integer of 0 or more.

8. Use of a photosensitive surface treatment liquid in the surface treatment method according to any one of claims 1 to 4,

the photoacid generator (B) generates a strong acid having a pKa of 1 or less,

CH₂＝CR²-(R³)_a-CO-R⁴···(A2)

-NH-R¹···(A1)

CH₂＝CR²-(R³)_a-SO₃X···(A2-1)

A¹-SiR¹⁰R¹¹-O-(-SiR¹⁰A²-O-)_p-SiR¹⁰R¹¹A³···(A6)